Process of removing hcn from flue gas

ABSTRACT

The invention includes a process for reducing the amount of HCN discharged to atmosphere from a FCC unit, having a regenerator and a means for collecting and supporting catalyst particles. The process comprises adding a catalyst to the regenerator flue gas prior to entering the collecting means and precipitating the catalyst in the collecting means to form a catalyst bed. Ammonia or ammonia precursor is optionally added to the flue gas. The flue gas HCN is reacted in the presence of water and oxygen in the flue gas, and optional ammonia or ammonia precursor, at 200° C. to 800° C. in the presence of the catalyst bed to reduce the HCN amount, and the flue gas containing a reduced amount of HCN is discharged to atmosphere. The catalyst is one or more supported transition or lanthanide metal catalysts. The process can also be utilized in any combustion process.

FIELD OF THE INVENTION

The invention relates to a process of reducing the amount of hydrogen cyanide discharged to atmosphere from a fluid catalytic cracking unit or any combustion process.

BACKGROUND OF THE INVENTION

The fluid catalytic cracking (FCC) process is a source of hydrogen cyanide (HCN) gas emissions in petroleum refining. In the FCC process, heavy hydrocarbon fractions are cracked to produce lighter, valuable products (gasoline, distillate, and C₂-C₄ olefins and saturated hydrocarbons). The cracking process takes place in the riser section of a FCC unit, where the hydrocarbon fractions are contacted with a FCC catalyst and other additive particles at elevated temperature. As the endothermic cracking reactions occur, coke (containing carbon, sulfur and nitrogen, among other components) is deposited onto the FCC catalyst and any additive particles. These particles are carried from the FCC unit's reactor to the catalyst regenerator, and the coke is burned off to form carbon monoxide, carbon dioxide, and a wide-range of gaseous sulphur and nitrogen species, e.g., SO₂, SO₃, COS, H₂S, N₂, NO, N₂O, NO₂, NH₃, and HCN.

The exact composition of these gases in the flue gas depends upon the detailed reaction conditions in the regenerator. For example, under full-burn conditions (excess oxygen used in combustion of coke) the main species are SO₂, SO₃, N₂ and NO. Under partial-burn conditions (sub-stoichiometric oxygen levels) much higher levels of the “reduced” S and N species (COS, H₂S, NH₃, HCN) may also be present. Most partial-burn FCC units will have a CO-boiler (COB) downstream to convert the CO to CO₂ in order to control CO emissions and recover the energy for steam production. Most of the reduced S and N species in the flue gas are converted to more highly oxidized forms in the CO-boiler. So COS and H₂S are converted to SO₂ and SO₃; and NH₃ and HCN are converted to N₂, NO, N₂O, and NO₂. Therefore, in both full-burn and partial-burn operations, the flue gas contaminants are predominantly sulfur oxide gases (e.g., SO₂ and SO₃ which are often collectively referred to as “SO_(x)” gases) and nitrogen oxide gases (e.g, NO, N₂O, NO₂ which are often collectively referred to as “NO_(x)” gases).

As a thermodynamically unstable species under FCC conditions, most of the hydrogen cyanide is converted to NO_(x). However, a small portion will remain as hydrogen cyanide and will be emitted to the atmosphere since nitrogen chemistry is not at thermodynamic equilibrium, but is under kinetic control in the FCC units. Unless captured or removed, the hydrogen cyanide would be emitted to the atmosphere along with other flue gases.

Processes have been taught to remove or reduce the amount of NO_(x) and SO_(x) gases discharged to atmosphere from a FCC unit, but little effort has been made for reducing the amount of hydrogen cyanide discharged to atmosphere. One method to remove NO_(x) gases has been to use ammonia as a reductant to reduce the NO_(x) to from nitrogen. See, for example, U.S. Pat. No. 4,778,665 which teaches the reduction of NO_(x) with ammonia in the presence of a crystalline zeolite catalyst. U.S. Pat. No. 4,778,665 teaches that at an appropriate point downstream of the ammonia injection, after reduction of the NO_(x), the particles are recovered by a cyclone separator or by an electrostatic precipitator, and the flue gas then is discharged.

It is desirable to reduce emissions of HCN gas in the effluent from an FCC unit.

SUMMARY OF THE INVENTION

The invention includes a process for reducing the amount of hydrogen cyanide (HCN) discharged to atmosphere from a fluid catalytic cracking (FCC) unit. A HCN-containing flue gas is discharged from the regenerator of the FCC unit and is then passed to a collecting means for collecting and supporting catalyst particles. The HCN-containing flue gas contains a small amount of oxygen and water. The process comprises adding a catalyst to the HCN-containing flue gas prior to the collecting means and precipitating the catalyst in the collecting means to form a catalyst bed in the collecting means. Ammonia or an ammonia precursor is optionally added to the flue gas prior to the collecting means and/or added to the flue gas within the collecting means. HCN in the flue gas is reacted with oxygen and water in the flue gas, and the optional ammonia or ammonia precursor, at a temperature ranging from 200° C. to 800° C. in the presence of the catalyst bed to reduce the amount of HCN in the flue gas, and the flue gas containing a reduced amount of HCN is discharged to atmosphere. The catalyst is one or more supported transition or lanthanide metal catalysts. The process can also be utilized to remove NO_(x) from any combustion process.

DETAILED DESCRIPTION OF THE INVENTION

The invention includes a process for reducing the amount of hydrogen cyanide (HCN) discharged to atmosphere from a fluid catalytic cracking unit. The FCC unit comprises a regenerator and a collecting means for collecting and supporting catalyst particles, wherein a HCN-containing flue gas is discharged from the regenerator and is then passed to the collecting means.

A typical FCC unit comprises a riser/reaction section in which FCC catalyst particles contact and vaporize a hydrocarbon feedstock entering the bottom of the riser of the FCC unit. The vaporized hydrocarbon carries the FCC catalyst up the riser into the reactor section. Cracked hydrocarbon product exits the top of the reactor and FCC catalyst particles are retained in a bed of particles in the lower part of the reactor. During cracking of the hydrocarbon, coke is deposited on the FCC catalyst.

The coked FCC catalyst is then passed to the regenerator of the FCC unit. As used in this application, the term “regenerator” also includes the combination of a regenerator and a CO boiler, particularly when the regenerator itself is run under partial burn conditions. In the regenerator, coke on the FCC catalyst is burned off in a fluidized bed in the presence of oxygen and a fluidization gas which are typically supplied by entering the bottom of the regenerator. The regenerated FCC catalyst is withdrawn from the fluidized bed and returned to the riser for reuse in the cracking process.

Since the coke generally contains some nitrogen compounds, when the coke is burned in the regenerator nitrogen oxides (i.e., NO, NO₂, etc., collectively known as NO_(x)) and HCN as an intermediate are formed. Unless some means is provided to control the release of the HCN from the regenerator, they will be exhausted to atmosphere along with the other combustion gases in the flue gas. The flue gas from the regenerator of an FCC unit will typically contain between greater than 10 ppm of HCN.

The HCN-containing flue gas (typically also containing some oxygen along with the other combustion gases) exiting the regenerator will typically carry entrained catalyst fines. A collecting means for collecting the catalyst fines (e.g., an electrostatic precipitator) is usually included in a FCC unit in order to collect catalyst fines so that they are not released to the atmosphere.

In the process of the invention, the HCN-containing flue gas is discharged from the regenerator and is then passed to the collecting means. A catalyst is added to the flue gas prior to entering the collecting means. The catalyst is one or more supported transition or lanthanide metal catalysts. Although not critical for the invention, the mean particle size of the catalyst particles useful in the invention are preferably from 1 μm to 200 μm, more preferably from 10 μm to 100 μm.

The supported transition or lanthanide metal catalyst comprises one or more transition or lanthanide metals and one or more supports. The transition metal includes any Group 3-12 transition metal. The transition or lanthanide metal is preferably vanadium, tungsten, iron, platinum, copper, or mixtures thereof.

The support is preferably an inorganic oxide and most commonly includes the oxides of Groups 2, 3, 4, 5, 13 and 14 elements. Useful inorganic oxide supports preferably have specific surface areas in the range 10 to 700 m²/g, pore volumes in the range 0.1 to 4 mL/g, and pore diameters from about 10 to 1000 Angstroms (1 to 100 nm). The inorganic oxide support is preferably magnesia, alumina, silica, titania, zirconia, ceria, niobia, tantalum oxides, molybdenum oxides, tungsten oxides, or mixed oxides or composite oxides of any two or more thereof, e.g. magnesia-alumina, silica-alumina, or titania-silica.

The support is preferably a hydrotalcite, a clay, or a zeolite. Suitable clays include halloysites, rectorites, hectorites, montmorillinites, synthetic montmorillinites, sepiolites, activated sepiolites, and kaolins. Suitable zeolites may be any natural or a synthetic zeolite, including molecular sieves, and is preferably composed of aluminum, silicon, and/or phosphorus. The zeolites typically have a three-dimensional arrangement of SiO₄, AlO₄, and/or PO₄ that are joined by the sharing of oxygen atoms. The zeolite frameworks are typically anionic, which are counterbalanced by charge compensating cations, typically alkali and alkaline earth elements (e.g., Na, K, Mg, Ca, Sr, and Ba) and also protons. Other metals (e.g., Fe, Ti, and Ga) may be incorporated into the framework of the zeolite to produce a metal-incorporated zeolite, e.g., titanium silicalite. The zeolite is preferably a beta zeolite, a faujasite (such as an X-zeolite or a Y-zeolite, including NaY and USY), an L-zeolite, a ZSM zeolite (e.g., ZSM-5, ZSM-48), an SSZ-zeolite (e.g., SSZ-13, SSZ-41, SSZ-33), a mordenite, a chabazite, an offretite, an erionite, a clinoptilolite, a silicalite, an aluminum phosphate zeolite (including metalloaluminophosphates such as SAPO-34), a mesoporous zeolite (e.g., MCM-41, MCM-49, SBA-15), a metal-incorporated zeolite, or mixtures thereof; more preferably, the zeolites are beta zeolite, ZSM-5 zeolite, or SSZ-33, or Y-zeolite. The zeolite is most preferably beta zeolite or ZSM-5 zeolite.

The hydrotalcite may be a hydrotalcite or hydrotalcite-like material (HTL). The hydrotalcite or HTL may be collapsed, dehydrated and or dehydroxylated. Non-limiting examples and methods for making various types of HTL are described in U.S. Pat. No. 6,028,023; U.S. Pat. No. 6,479,421; U.S. Pat. No. 6,929,736; and U.S. Pat. No. 7,112,313; which are incorporated by reference herein in their entirety. Other non-limiting examples and methods for making various types of HTL are described in U.S. Pat. No. 4,866,019; U.S. Pat. No. 4,964,581; and U.S. Pat. No. 4,952,382; which are incorporated by reference herein in their entirety. Preferably, the hydrotalcite is a magnesia-alumina hydrotalcite.

Alumina is also a preferred support. The alumina is a solid material that contains a major proportion of aluminum oxide. Amorphous (i.e., non-crystalline) aluminum oxides are particularly preferred for use. In general, suitable aluminas are further characterized by having a relatively large surface area in relation to their mass, preferably the average specific surface area is from 1 m²/g to 1000 m²/g, and most preferably from about 50 m²/g to 500 m²/g. “Specific surface area” is used normally in the art and expresses the relationship of surface area to mass. Preferred aluminas include α-alumina, γ-alumina, and activated aluminas. Activated aluminas are partially hydroxylated aluminum oxide whose chemical compositions can be represented by the formula Al₂O_((3-x))(OH)_(2x), where x ranges from about 0 to 0.8. Activated aluminas are particularly preferred.

Preferably, the amount of transition or lanthanide metal present in the supported transition or lanthanide metal catalyst will be in the range of from 0.01 to 30 weight percent. When the transition metal is a noble metal such as palladium, platinum, gold, silver, iridium, rhenium, ruthenium, and osmium, the amount of transition metal is more preferably from 0.01 to 10 weight percent, most preferably 0.02 to 5 weight percent. For lanthanide metals and transition metals other than the noble metals, the amount of transition metal present in the supported transition or lanthanide metal catalyst is more preferably 2.5 to 25 weight percent. The manner in which the transition or lanthanide metal is incorporated onto the support is not considered to be particularly critical. For example, a transition or lanthanide metal compound (e.g., copper nitrate) may be supported on a hydrotalcite by impregnation, adsorption, incipient wetness, ion-exchange, precipitation, or the like.

Preferred supported transition or lanthanide metal catalysts include a supported platinum catalyst. The supported platinum catalyst preferably comprises platinum and an inorganic oxide; and more preferably comprises platinum on alumina. Preferred supported transition or lanthanide metal catalysts also comprise (a) vanadium, tungsten, copper, iron, cerium, or mixtures thereof, and (b) a hydrotalcite, a clay, or a zeolite; and more preferably comprises copper and a hydrotalcite. Because the flue gas may contain sulfur oxides, it may be preferable to avoid the use of noble metal-containing catalysts (such as platinum and palladium) since they may be subject to sulfur poisoning.

After the addition of the catalyst to the HCN-containing flue gas, the catalyst is then collected in the collecting means to form a catalyst bed in the collecting means. Suitable collecting means include an electrostatic precipitator, a filter, a pebble bed, a third stage separator, and the like. Suitable filters include a bag filter and a sintered metal filter. Preferred collecting means include an electrostatic precipitator, a bag filter and a sintered metal filter. In the case of an electrostatic precipitator (ESP), the catalyst collects on plates contained in the ESP and forms a catalyst bed within the ESP. The plates also serve as a support for the catalyst to aid in contacting the HCN-containing flue gas with the catalyst.

Another preferred collecting means includes a combination of a fast fluidized bed and a cyclone. The fast fluidized bed may be a wide point in the flue gas exit line that will contain a dilute number of catalyst particles that act as the fluidized bed. The fast fluidized bed allows particles entrained in the flue gas stream exiting the FCC regenerator to pass through the vessel without increasing pressure drop. The cyclone acts to prevent catalyst from exiting the FCC unit and being emitted to atmosphere, while allowing fines to exit the process. The catalyst particles trapped by the cyclone can be added back into the fast fluidized bed.

Preferably, an additional contact unit is added prior to or after the collecting means in order to ensure good contact between the additive and flue gas.

Ammonia or an ammonia precursor optionally is added to the flue gas. Suitable ammonia precursors include urea, ammonium carbonate, ammonium carbamate, ammonium hydrogen carbonate, and ammonium formate. The ammonia or ammonia precursor can be introduced to the flue gas prior to entering the collecting means and/or within the collecting means. If utilized, the ammonia or ammonia precursor is preferably introduced into the flue gas at a point prior to the collecting means to allow good mixing of the ammonia or ammonia precursor in the flue gas to occur. If ammonia or an ammonia precursor is added to the flue gas, the ammonia or ammonia precursor and the catalyst are preferably added at the same location to the flue gas.

The amount of ammonia or ammonia precursor added in the flue gas is not considered critical, but preferably the molar ratio of ammonia to HCN is in the range of 0.05 to 1.0, more preferably 0.1 to 0.5, so that preferably 5 to 100 percent and more preferably at least 60 percent, reduction of HCN can be achieved.

Although the presence of oxygen and water is necessary for the reduction of the amount of hydrogen cyanide in accordance with the invention, sufficient free oxygen and water generally remain mixed with the combustion gases leaving the regenerator for the process to occur. Additional oxygen or water can be added if insufficient amounts are present, as for example where the regenerator is operated in an oxygen lean mode.

The HCN in the flue gas is reacted with the oxygen and water in the presence of the catalyst bed in the collecting means to reduce the amount of HCN in the flue gas. Preferably, the reaction occurs at a temperature at a temperature ranging from 200° C. to 800° C., more preferably from 200° C. to 500° C. It is believed that the complete reaction of HCN results in the production of N₂. However, it is possible that not all of the HCN will be converted to N₂. For instance, NO may be produced due to the presence of insufficient water in the flue gas. The preferred injection of ammonia or ammonia precursor can be used to control the emission of the by-product NO_(x) during the process, by the reduction of the by-product NO with NH₃ over the catalyst bed. Thus, a flue gas having a reduced amount of HCN results and it is then discharged to atmosphere.

It may be preferable to cool the flue gas prior to the collecting means. Any suitable cooling means may be utilized, including heat exchangers. The addition of the ammonia or ammonia precursor, along with possible diluent gases, may cool the flue gas prior to the collecting means. Preferably, the gases are cooled prior to the point of introducing the ammonia or ammonia precursor to minimize spontaneous combustion of the ammonia or ammonia precursor.

The process of the invention may also be used to reduce HCN emissions from any combustion process that produces HCN. Thus, the invention also includes a process for reducing the amount of hydrogen cyanide discharged to atmosphere from a combustion process. The combustion process comprises a combustion unit and a collecting means for collecting and supporting catalyst particles. The flue gas containing HCN that is discharged from the combustion unit is passed to the collecting means. The process comprises adding a catalyst to the flue gas prior to entering the collecting means, and then precipitating the catalyst in the collecting means to form a catalyst bed in the collecting means. Ammonia or an ammonia precursor is optionally added to the flue gas prior to entering the collecting means, to the flue gas within the collecting means, or both. The HCN in the flue gas is reacted in the presence of water and oxygen in the flue gas, and the optional ammonia or ammonia precursor, at a temperature ranging from 200° C. to 800° C. in the presence of the catalyst bed to reduce the amount of HCN in the flue gas, and the flue gas containing a reduced amount of HCN is discharged to atmosphere. All of these process steps are the same as described above.

The catalyst is one or more supported transition or lanthanide metal catalysts, as described above. The combustion unit is preferably a coal combustion unit, a fuel oil combustion unit, a wood product combustion unit, a fluid catalytic cracking unit, a fired heater, an ethylene heater, a hydrogen heater or the like.

The following examples merely illustrate the invention. Those skilled in the art will recognize many variations that are within the spirit of the invention and scope of the claims.

Example 1 Preparation of Catalysts

Catalyst 1A: CuO on Hydrotalcite-Like Material

Transition or lanthanide metals can be added to hydrotalcite-like materials as follows: A copper nitrate solution (1082 g, containing 16.76 wt. % solid) is added to a slurry of a MgO and Al₂O₃ mixture (6771 g, Mg/Al molar ratio 3/1). The mixture is stirred for 1 hour at room temperature, and the resulting mixture is then spray dried and calcined at 500° C. Catalyst 1A contains approximately 26 wt. % Al₂O₃, 55 wt. % MgO, and 19 wt. % CuO.

Catalyst 1B: Pt/Al₂O₃

Pt is added to Al₂O₃ as follows: An aqueous Pt(NH₃)₂Cl₂ solution (containing 0.137 g Pt(NH₃)₂Cl₂ (containing 54.8 wt. % solid) in 19.8 g H₂O) is sprayed onto Al₂O₃ (116 g). The resulting material is then dried at 120° C. and calcined at 500° C. Catalyst 1B contains approximately 0.06 wt. % Pt.

Catalyst 1C: Fe₂O₃ and CeO₂ on Hydrotalcite-Like Material

Catalyst 1C can be prepared according to the procedure of Catalyst 1A except that iron nitrate and cerium nitrate are used in place of the copper nitrate solution. Catalyst 1A contains approximately 21 wt. % Al₂O₃, 53 wt. % MgO, 10 wt. % Fe₂O₃, and 16 wt. % CeO₂.

Catalyst 1D: Pd/Al₂O₃

Catalyst 1D is prepared according to the procedure of Catalyst 1B except that Pd(NH₃)₂Cl₂ is used in place of the Pd(NH₃)₂Cl₂ solution. Catalyst 1D contains approximately 0.06 wt. % Pt.

Catalyst 1E: V₂O₅/TiO₂

Catalyst 1E is a commercial selective catalytic reduction catalyst containing approximately 85 wt. % TiO₂, 2.5 wt. % V₂O₅, and 9 wt. % SiO₂.

Catalyst 1F: Pd/Al₂O₃+CuO/HT

Catalyst 1F is prepared by mixing 90 wt. % 1D and 10 wt. % 1A.

The physical properties of the catalysts are listed in Table 1.

Example 2 HCN Reduction Tests

The catalysts of Example 1 are tested in a fix bed quartz reactor. A gas mixture (260 cc/min), containing 125 ppm HCN, 0.9 vol. % O₂, 1.2 vol. % CO, 1 vol. % H₂O, and the balance helium, is contacted with a fixed bed of 2.0 g catalyst mixture, containing 1 wt. % of Example 1 catalyst mixed with a spent FCC catalyst. The effluent gas was analyzed on-line by a mass spectrometer and/or IR analyzer, and the temperature of the catalyst bed was monitored by an Omega temperature logger. The conversion of HCN at four temperatures is shown in Table 2, and compared to a run without any HCN removal catalyst (only spent FCC catalyst). The results show that the mixture of Pd/Al₂O₃ and CuO/HTLP is more effective for the removal of HCN.

TABLE 1 Physical properties of catalysts Average Particle Size Surface Area Catalyst (μm) (m²/g) 1A 50 118 1B 72 91 1C 68 127 1D 71 105 1E — — 1F — —

TABLE 2 Testing Results HCN Conversion (%) Catalyst 250° C. 350° C. 450° C. 550° C. none * 20 40 56 76 1B 27 51 93 98 1F 38 84 97 99 * Comparison Example 

We claim:
 1. A process for reducing the amount of hydrogen cyanide (HCN) discharged to atmosphere from a fluid catalytic cracking unit comprising a regenerator and a collecting means for collecting and supporting catalyst particles, wherein a flue gas containing HCN is discharged from the regenerator and is then passed to the collecting means, said process comprising: (a) adding a catalyst to the flue gas prior to entering the collecting means; (b) precipitating the catalyst in the collecting means to form a catalyst bed in the collecting means; (c) optionally, adding ammonia or an ammonia precursor to the flue gas prior to entering the collecting means, to the flue gas within the collecting means, or both; (d) reacting HCN in the flue gas in the presence of water and oxygen in the flue gas, and optional ammonia or ammonia precursor, at a temperature ranging from 200° C. to 800° C. in the presence of the catalyst bed to reduce the amount of HCN in the flue gas; and (e) discharging the flue gas containing a reduced amount of HCN to atmosphere, wherein the catalyst is one or more supported transition or lanthanide metal catalysts.
 2. The process of claim 1 wherein the flue gas is cooled prior to entering the collecting means.
 3. The process of claim 1 wherein the collecting means is an electrostatic precipitator.
 4. The process of claim 1 wherein the collecting means is a bag filter.
 5. The process of claim 1 wherein the collecting means is a sintered metal filter.
 6. The process of claim 1 wherein the collecting means is a combination of a fast fluidized bed and a cyclone.
 7. The process of claim 1 wherein the supported transition or lanthanide metal catalyst is a supported platinum catalyst.
 8. The process of claim 7 wherein the supported platinum catalyst comprises platinum and an inorganic oxide.
 9. The process of claim 8 wherein the supported platinum catalyst comprises platinum on alumina.
 10. The process of claim 1 wherein the supported transition or lanthanide metal catalyst comprises (a) vanadium, tungsten, copper, iron, cerium, or mixtures thereof, and (b) a hydrotalcite, a clay, or a zeolite.
 11. The process of claim 10 wherein the supported transition or lanthanide metal catalyst comprises copper and a hydrotalcite.
 12. The process of claim 1 wherein HCN in the flue gas is reacted with water and oxygen, and optional ammonia or ammonia precursor, at a temperature ranging from 200° C. to 500° C.
 13. The process of claim 1 wherein the catalyst has a mean particle size of 10 μm to 100 μm.
 14. A process for reducing the amount of hydrogen cyanide (HCN) discharged to atmosphere from a combustion process comprising a combustion unit and a collecting means for collecting and supporting catalyst particles, wherein a flue gas containing HCN is discharged from the combustion unit and is then passed to the collecting means, said process comprising: (a) adding a catalyst to the flue gas prior to entering the collecting means; (b) precipitating the catalyst in the collecting means to form a catalyst bed in the collecting means; (c) optionally, adding ammonia or an ammonia precursor to the flue gas prior to entering the collecting means, to the flue gas within the collecting means, or both; (d) reacting HCN in the flue gas in the presence of water and oxygen in the flue gas, and optional ammonia or ammonia precursor, at a temperature ranging from 200° C. to 800° C. in the presence of the catalyst bed to reduce the amount of HCN in the flue gas; and (e) discharging the flue gas containing a reduced amount of HCN to atmosphere, wherein the catalyst is one or more supported transition or lanthanide metal catalysts.
 15. The process of claim 14 wherein the combustion unit is a coal combustion unit, a fuel oil combustion unit, a wood product combustion unit, a fluid catalytic cracking unit, a fired heater, an ethylene heater, or a hydrogen heater. 